EP3551675B1 - Compositions de résine - Google Patents

Compositions de résine Download PDF

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Publication number
EP3551675B1
EP3551675B1 EP17729959.1A EP17729959A EP3551675B1 EP 3551675 B1 EP3551675 B1 EP 3551675B1 EP 17729959 A EP17729959 A EP 17729959A EP 3551675 B1 EP3551675 B1 EP 3551675B1
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Prior art keywords
examples
group
resin
carbon atoms
polymerization
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German (de)
English (en)
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EP3551675A1 (fr
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Sajal Das
Paul Boothe
Patrick SHIPMAN
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Novoset LLC
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Novoset LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/22—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having three or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/58—[b]- or [c]-condensed
    • C07D209/72—4,7-Endo-alkylene-iso-indoles
    • C07D209/76—4,7-Endo-alkylene-iso-indoles with oxygen atoms in positions 1 and 3
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/20—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F32/02—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F32/06—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
    • H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits

Definitions

  • thermosetting resin compositions according to claim 1 that are useful for the next-generation wireless standard (i.e. namely 5th generation mobile networks or "5G").
  • 5G is the follow-up to the current wireless standard known as 4G or long term evolution (LTE). It is believed to be able to enable data transmission rates of more than 10 Gbps or 100 times the throughput of LTE.
  • LTE long term evolution
  • 5G technology consists of three separate elements - enhanced mobile broadband (1,000 times more capacity and one-tenth the latency), the Internet of Things (IOT) and other Wi-Fi based technology, and machine-to-machine (M2M) type communications.
  • IOT Internet of Things
  • M2M machine-to-machine
  • Today's LTE networks (servers, router base station, etc.) are believed to operate from 700 MHz to 3.5 GHz. In comparison, 5G will not only co-exist with LTE, but will also operate in unlicensed or millimeter wave bands. This involves the spectrum band between 30 GHz and 300 GHz, which in turn enables more data capabilities.
  • next-generation technologies have higher performance requirements that cannot be achieved with many of the composite materials currently used in device production.
  • the higher signal intensities required for 5G technologies will demand new composite materials that can maintain signal integrity (e.g. very low dielectric loss) and small circuit size (e.g. low dielectric constant) while maintaining the thermal, physical and mechanical properties desirable for PCB and other mobile devices.
  • US 3,560,583 A discloses a process for preparing substituted cyclopentadienes.
  • the present invention provides a resin according to claim 1.
  • the resin has the structure:
  • the resins of Formula (VI) may be reacted with a dienophile or heterodienophile.
  • the resins of Formula (VI) may be reacted with a compound having a maleimide group.
  • the resins of Formula (VI) may be reacted with bis-maleimide or an analog or derivative thereof.
  • the resins of Formula (VI) may be reacted with benzoquinone or an analog or derivative thereof.
  • the resins of Formula (VI) may be reacted with an acrylate.
  • low dielectric materials having such characteristics which particularly useful as materials for use in the aerospace industry, communications industry, and electronics industry.
  • the resins, polymers, blends, etc. disclosed herein may be used in printed circuit boards, as substrates for integrated circuits, or as substrates or packaging for other microelectronic circuits or applications.
  • kits comprising any of the resins, polymers, blends, etc. disclosed herein.
  • the resins, polymers, blends, etc. may be mixed with a suitable solvent.
  • the kits may comprise multiple resins, polymers, blends, etc., where each of the resins, polymers, blends, etc. are provided in a separate container.
  • the kits may include a resin and other reactants, reagents, or solvents.
  • the kits may further comprise instructions.
  • the resins, polymers, copolymers, and compositions described herein have a dielectric value ranging from about 1.5 to about 3, and/or a dissipation value ranging from about 0.0001 to about 0.004, allowing the resins, polymers, copolymers, and compositions to be materials suitable for use various applications across many industries.
  • the resins, polymers, copolymers, and compositions are suitable for use in high speed communications applications (e.g. 5G communication systems, devices, and networks).
  • An object of the disclosure is to provide a dielectric material with low dielectric loss, which has excellent dielectric properties, low coefficient of thermal expansion and low water absorption.
  • variable e.g. "w”
  • each use of the variable in the formula or chemical structure is independent from any other use, unless explicitly noted otherwise.
  • each ⁇ w′′′ may be the same or different, i.e. if "w” is defined as 0 or an integer ranging from 1 to 150, each "w” may independently be selected from 0 or an integer ranging from 1 to 150.
  • each R 5 may independently be selected from -CH- or -C-R 12 .
  • Ranges may be expressed herein as from “about” one particular value, and/or to "about” another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
  • the phrase "at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements.
  • This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase "at least one" refers, whether related or unrelated to those elements specifically identified.
  • “at least one of A and B" can refer, in one example, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another example, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another example, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.
  • a method involving steps a, b, and c means that the method includes at least steps a, b, and c.
  • steps and processes may be outlined herein in a particular order, the skilled artisan will recognize that the ordering steps and processes may vary.
  • alkyl refers to a straight or branched hydrocarbon chain that comprises a fully saturated (no double or triple bonds) hydrocarbon group.
  • the alkyl group may have 1 to 20 carbon atoms (whenever it appears herein, a numerical range such as “1 to 20” refers to each integer in the given range; e.g., "1 to 20 carbon atoms” means that the alkyl group may consist of 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to and including 20 carbon atoms, although the present definition also covers the occurrence of the term "alkyl” where no numerical range is designated).
  • the alkyl group of the compounds may be designated as "C 1 -C 4 alkyl” or similar designations.
  • “C 1 -C 4 alkyl” indicates that there are one to four carbon atoms in the alkyl chain, i.e., the alkyl chain is selected from methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.
  • Typical alkyl groups include, but are in no way limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tertiary butyl, pentyl and hexyl.
  • the alkyl group may be substituted or unsubstituted.
  • alkenyl refers to an alkyl group that contains in the straight or branched hydrocarbon chain one or more double bonds.
  • An alkenyl group may be unsubstituted or substituted.
  • alkynyl refers to an alkyl group that contains in the straight or branched hydrocarbon chain one or more triple bonds.
  • An alkynyl group may be unsubstituted or substituted.
  • aryl means an aromatic carbocyclic radical or a substituted carbocyclic radical containing preferably from 6 to 10 carbon atoms, such as phenyl or naphtyl or phenyl or naphtyl, optionally substituted by at least one of the substituents selected in the group constituted by alkyl, alkenyl, alkynyl, aryl, aralkyl, hydroxy, alkoxy, aryloxy, aralkoxy, carboxy, aroyl, halo, nitro, trihalomethyl, cyano, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, acylamino, aroylamino, carbamoyl, alkylcarbamoyl, dialkylcarbamoyl, alkylthio, arylthio, alkylene or -NYY′ where Y and Y′ are independently hydrogen, alkyl, aryl
  • the term "blend” refers to a mixture of two or more different species of resins or a resin and another polymer or copolymer.
  • curing refers to processes of hardening a resin material.
  • cycloalkyl or like terms (e.g. a cyclic alkyl group) refer to a completely saturated (no double or triple bonds) mono- or multi-cyclic hydrocarbon ring system. When composed of two or more rings, the rings may be joined together in a fused fashion. Cycloalkyl groups can contain 3 to 10 atoms in the ring(s) or 3 to 8 atoms in the ring(s). A cycloalkyl group may be unsubstituted or substituted.
  • Typical cycloalkyl groups include, but are in no way limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Ca to Cb in which "a” and “b” are integers refer to the number of carbon atoms in an alkyl, alkenyl or alkynyl group, or the number of carbon atoms in the ring of a cycloalkyl, cycloalkenyl, cycloalkynyl or aryl group, or the total number of carbon atoms and heteroatoms in a heteroalkyl, heterocyclyl, heteroaryl or heteroalicyclyl group.
  • the alkyl, alkenyl, alkynyl, ring of the cycloalkyl, ring of the cycloalkenyl, ring of the cycloalkynyl, ring of the aryl, ring of the heteroaryl or ring of the heteroalicyclyl can contain from "a" to "b", inclusive, carbon atoms.
  • a "C 1 to C 4 alkyl” group refers to all alkyl groups having from 1 to 4 carbons, that is, CH 3 -, CH 3 CH 2 -, CH 3 CH 2 CH 2 -, (CH 3 ) 2 CH-, CH 3 CH 2 CH 2 CH 2 -, CH 3 CH 2 CH(CH 3 )- and (CH 3 ) 3 C-. If no "a” and "b” are designated with regard to an alkyl, alkenyl, alkynyl, cycloalkyl cycloalkenyl, cycloalkynyl, aryl, heteroaryl or heteroalicyclyl group, the broadest range described in these definitions is to be assumed.
  • an IPN refers to a polymeric system comprising two or more networks which are at least partially interlaced on a molecular scale, to form both chemical and physical bonds between the networks.
  • the networks of an IPN cannot be separated unless chemical bonds are broken.
  • an IPN structure represents two or more polymer networks that are partially chemically cross-linked and/or partially physically entangled.
  • polymer is defined as being inclusive of homopolymers, copolymers, interpenetrating networks, and oligomers. Thus, the term polymer may be used interchangeably herein with the term homopolymers, copolymers, interpenetrating polymer networks, etc.
  • homopolymer is defined as a polymer derived from a single species of monomer.
  • copolymer is defined as a polymer derived from more than one species of monomer, including copolymers that are obtained by copolymerization of two monomer species, those obtained from three monomers species (“terpolymers”), those obtained from four monomers species (“quaterpolymers”), etc.
  • oligomer is defined as a low molecular weight polymer in which the number of repeating units does not exceed twenty.
  • copolymer is further defined as being inclusive of random copolymers, alternating copolymers, graft copolymers, and block copolymers. Copolymers, as that term is used generally, include interpenetrating polymer networks.
  • random copolymer is defined as a copolymer comprising macromolecules in which the probability of finding a given monomeric unit at any given site in the chain is independent of the nature of the adjacent units. In a random copolymer, the sequence distribution of monomeric units follows Bernoullian statistics.
  • alternating copolymer is defined as a copolymer comprising macromolecules that include two species of monomeric units in alternating sequence.
  • the indicated “optionally substituted” or “substituted” group may be substituted with one or more group(s) individually and independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl, heteroaryl, heteroalicyclyl, aralkyl, heteroaralkyl, (heteroalicyclyl)alkyl, hydroxy, protected hydroxyl, alkoxy, aryloxy, acyl, mercapto, alkylthio, arylthio, cyano, cyanate, halogen, thiocarbonyl, O-carbamyl, N-carbamyl, O-thiocarbamyl, N-thiocarbamyl, C-amido, N-amido, S-sulfonamido, N-sulfonamido, C-carboxy, protected C-car
  • any of the above groups may include one or more heteroatoms, including O, N, or S.
  • that alkyl group may comprise a heteroatom selected from O, N, or S (e.g. -(CH 2 -CH 2 -O-CH 2 -CH 2 )-).
  • prepreg refers to a reinforcing fabric which has been preimpregnated with a resin system.
  • Resins or Compositions Comprising More Than One Resin
  • the present disclosure provides resins, including resins defined by Formulas (IA) and (IB).
  • the present disclosure also provides compositions comprising mixtures of the resins of Formulas (IA) and (IB).
  • a composition may comprise a first resin of Formula (IA) and a second resin of Formula (IB), wherein the first and second resins differ in at least one substituent or moiety or in the number of any repeating groups.
  • any composition may comprise any number of resins of Formulas (IA) or (IB), and any of the different resins may be present in the same or differing amounts within the composition.
  • a composition may comprise a first resin of Formulas (IA) or (IB), a second resin of Formulas (IA) or (IB), and a third resin of Formulas (IA) or (IB), wherein each of the first, second, and third resins differ in at least one substituent, and where the first resin is present in an amount ranging from between about 20% to about 40% by weight of the composition, the second resin is present in an amount ranging from 10% to about 30% by weight of the composition, and the third resin constitutes the remainder of the composition by weight of the composition.
  • any of the resins of Formulas (IA) or (IB) may differ from one another, it is meant that the resins may differ (i) in any moiety constituting the resin; (ii) the number of any of the repeat groups of the moiety that are present, (iii) the positioning of any moiety along any cyclic or aromatic group; and/or (iv) isomeric or stereochemical differences between the various moieties and/or groups.
  • any group X may be substituted with any number of A groups as denoted in Formulas (IA) and (IB).
  • each of the A groups may be the same or different.
  • X is derived from cyclopentadiene and m is 2
  • X may be substituted with a first A group and with a second A group, where the first and second A groups are different.
  • different X groups may comprise a same or a different number of A groups and, of course, the same or different A groups, without limitation.
  • p is an integer ranging from 1 to 100. In other examples, p is an integer ranging from 1 to 75. In yet other examples, p is an integer ranging from 1 to 50. In further examples, p is an integer ranging from 1 to 20. In even further examples, p is an integer ranging from 1 to 10. In yet further examples, p is 0. In some examples, w is an integer ranging from 1 to 100. In other examples, w is an integer ranging from 1 to 75. In yet other examples, w is an integer ranging from 1 to 50. In further examples, w is an integer ranging from 1 to 20. In even further examples, w is an integer ranging from 1 to 10. In yet further examples, w is 0.
  • L is a halide or -OH. In other examples, L is selected from the group consisting of F, Cl, Br and -OH.
  • cyclopentadiene-based ring or “cyclopentadiene” (used interchangeably herein) is not limited to cyclopentadiene, but includes derivatives of cyclopentadiene, i.e. those containing substituents other than hydrogen, or those capable of being substituted with A groups as defined in Formulas (IA) or (IB).
  • cyclopentadiene-based ring or “cyclopentadiene” are also intended to include fused ring systems comprising, in part, a cyclopentadiene ring, e.g. an indene.
  • X may encompass cyclopentadiene; indene; an indene substituted with one or more C 1 to C 4 straight-chain or branched alkyl groups; fluorene; and fluorene substituted with one or more C 1 to C 4 straight-chain or branched alkyl groups.
  • X is a cyclopentadiene ring
  • this may refer to the base structure of X and, as will appreciated by those of ordinary skill in the art, any of the "implicit" hydrogens of the cyclopentadiene ring may be substituted with any number of A groups, as denoted in Formulas (IA) or (IB).
  • Each -X(A) r (Z) n - group may be the same or different.
  • each -X(A) m (Z) n -group may be the same or different.
  • the compounds of Formula (IA) or (IB) may comprise different -X(A) r (Z) n - groups or different -X(A) m (Z) n - groups, where each -X(A) r (Z) n - group or - X(A) m (Z) n - group is provided randomly, in blocks, or in random blocks.
  • the compounds of Formulas (IA) or (IB) may comprise two different -X(A) r (Z) n - groups, wherein at least one of the -X(A)r(Z)n- groups comprises a different (A) moiety.
  • the compounds of Formulas (IA) or (IB) may comprise a first -X(A) r (Z) n - group substituted with a vinyl benzyl group, and a second -X(A) r (Z) n - group substituted with an allyl group, where each of the first and second -X(A) r (Z) n - groups may be distributed randomly, in blocks, or in random blocks.
  • the compounds of Formulas (IA) or (IB) having different -X(A) r (Z) n - groups may have the structure provided by Formula (IC): where w and p are each independently an integer ranging from 1 to 150.
  • the resins of Formulas (IA) or (IB) may have two, three or more different - X(A)m(Z)n- groups or two, three, or more different -X(A) r (Z) n - groups, which may be provided randomly within the resin.
  • any two or more different -X(A)m(Z)n-groups or -X(A) r (Z) n - groups may differ in the (A) moiety included, the different -X(A) m (Z) n - groups or -X(A) r (Z) n - groups may instead differ by virtue of the (Z) group included, or any combination of (A) and/or (Z) groups.
  • A may have the structure defined by Formula (IIA):
  • T is -phenyl, or -CH 2 -phenyl
  • - CH CH-CH 3
  • alkyne group z is 1.
  • R 1 is -CH 2 -. In other examples, R 1 is -C(CH 3 ) 2 -.
  • A has the structure defined by Formula (IIB): wherein
  • v is 0 or 1.
  • R a , R b , R c , R d are independently selected from H, F, a C 1 to C 6 straight chain or branched alkyl group; a cyclopentadiene, -CH2-cyclopentadiene, or -CH 2 -CH 2 -cyclopentadiene.
  • Q is C, R a and R b are -CH 3 , R c and R d are H, u is 0, and Y is - CH3. In other examples, Q is C, R a and R b are -CH 3 , R c and R d are H, u is 0, Y is -CH 3 , and t is an integer ranging from 1 to 6.
  • Q is C
  • R a and R b are H
  • one of R c and R d is -CH 2 -CH 3 or -CH 3
  • the other of R c and R d is -CH 2 -CH 2 -CH 2 -CH 3 or -CH 2 -CH 2 -CH 2 -CH 3
  • u is 0, and Y is H.
  • Q is C
  • R a and R b are H
  • one of R c and R d is -CH 2 -CH 3 or -CH 3
  • the other of R c and R d is -CH 2 -CH 2 -CH 2 -CH 3 or -CH 2 -CH 2 -CH 2 -CH 3
  • u is
  • Y is H
  • t is an integer ranging from 1 to 6.
  • Q is C
  • R a and R b are H
  • one of R c and R d is -CH 2 -CH 3 or -CH 3
  • the other of R c and R d is -CH 2 -CH 2 -CH 2 -CH 3 or -CH 2 -CH 2 -CH 2 -CH 3
  • u is 0, and Y is - CH3.
  • Q is C
  • R a and R b are H
  • one of R c and R d is -CH 2 -CH 3 or -CH 3
  • the other of R c and R d is -CH 2 -CH 2 -CH 2 -CH 3 or -CH 2 -CH 2 -CH 2 -CH 3
  • u is 0,
  • Y is -CH 3
  • t is an integer ranging from 1 to 6.
  • Q is C, R a and R b are H, R c and R d are both -CH 3 , u is 0, and Y is H.
  • Q is C, R a and R b are H, R c and R d are both -CH 3 , u is 0, Y is H, and t is an integer ranging from 1 to 6.
  • Q is C, R a and R b are H, R c and R d are both - CH3, u is 0, and Y is -CH 3 .
  • Q is C, R a and R b are H, R c and R d are both -CH 3 , u is 0, Y is -CH 3 , and t is an integer ranging from 1 to 6.
  • Q is C, R a and R b are H, R c and R d are independently selected from a cyclopentadiene or -CH2-cyclopentadiene, u is 0, v is 1, and Y is CH 3 .
  • Q is C, R a and R b are H, R c and R d are independently selected from a cyclopentadiene or -CH 2 -cyclopentadiene, u is 0, v is 1, and Y is H.
  • A has the structure defined by Formula (IIC): wherein
  • T is -phenyl, or -CH 2 -phenyl
  • - CH CH-CH 3
  • alkyne z is 1.
  • the R a and R b are independently a C 1 to C 6 linear or cyclic, branched or straight chain aliphatic group. In some examples, the R a and R b are independently a C 1 to C 6 alkyl group. In some examples, the R a and R b are independently a C 1 to C 4 alkyl group.
  • t is 0, u is 1, and Y is alkyne.
  • u is 1 and T is phenyl.
  • t is 1, u is 1, T is phenyl, and R a and R b are both H.
  • R a and R b are independently a C 1 to C 6 linear or cyclic, branched or straight chain aliphatic group.
  • z is 1 or 2. In other examples, z is 1.
  • the R a and R b are independently a C 1 to C 6 alkyl group. In some examples, the R a and R b are independently a C 1 to C 4 alkyl group.
  • group Y may be present at any position(s) along the phenyl ring.
  • any resin of Formulas (IA) or (IB) may comprise different Y groups.
  • any resin of Formulas (IA) or (IB) may comprise the same Y group, but the Y group may be located at different positions along the phenyl ring.
  • some A groups may comprise a single Y group while other A groups may contain multiple Y groups, which may be the same or different or differ in their positioning.
  • Z has the structure defined by Formula (IIIA): wherein
  • R e and R f are independently selected from H or a straight chain or branched alkyl group having between 1 and 4 carbon atoms; and y is an integer ranging from between 1 and about 10. In other examples, R e and R f are independently selected from H or a straight chain alkyl group having between 1 and 4 carbon atoms; and y is an integer ranging from between 1 and about 6.
  • R e and R f are both H; and y is an integer ranging from between 1 and about 10. In further examples, R e and R f are both H; and y is an integer ranging from between 1 and about 6. In even further examples, R e and R f are both H; and y is an integer ranging from between 2 and about 6. In yet even further examples, R e and R f are both H; and y is an integer ranging from between 3 and about 6. In even further examples, R e and R f are both H; and y is 3. In even further examples, R e and R f are both H; and y is 6.
  • R e and R f are independently selected from H, -CH 2 -CH 3 , or - CH3. In other examples, one of R e and R f is selected from H or -CH 3 , and the other of R e and R f is H. In yet other examples, R e and R f are both H.
  • Z has the structure defined by Formula (IIIB): where y is an integer ranging from between 1 and about 20.In some examples of the moieties of Formula (IIIB), y ranges from 1 to 6. In some examples of the moieties of Formula (IIIB), y ranges from 1 to 4. In some examples of the moieties of Formula (IIIB), y ranges from 1 to 3. In some examples of the moieties of Formula (IIIB), y ranges from 2 to 6. In some examples of the moieties of Formula (IIIB), y ranges from 2 to 4.
  • Z has the structure defined by Formula (IIIC): where y is as defined above. In some examples of the moieties of Formula (IIIC), y ranges from 1 to 6. In some examples of the moieties of Formula (IIIC), y ranges from 1 to 4. In some examples of the moieties of Formula (IIIC), y ranges from 1 to 3. In some examples of the moieties of Formula (IIIC), y ranges from 2 to 6. In some examples of the moieties of Formula (IIIC), y ranges from 2 to 4.
  • the compounds of Formula (IA) or (IB) have the structure defined by Formulas (IVA), (IVB), or (IVC): or wherein
  • the A groups may be in any position along any of the cyclopentadiene-based group.
  • the A groups may be located on the same or different positions in each cyclopentadiene-based group.
  • one group may comprise an A group at a first ring position (e.g. one carbon away from the carbon bearing the Z n group) while another group may comprise an A group at a second or third ring position (e.g. two or three carbons away from the carbon bearing the Z n group).
  • one group may comprise an A group at a first ring position (e.g. one carbon away from the carbon bearing the Z n group) while another group may comprise an A group at a second or third ring position (e.g. two or three carbons away from the carbon bearing the Z n group).
  • m, p, q, and x are 0;
  • (Z) n is a straight-chain or branched aliphatic group having between 1 and 20 carbon atoms; o is 1; and L is a leaving group.
  • m, p, q, and x are 0;
  • (Z) n is a straight-chain or branched aliphatic group having between 1 and 10 carbon atoms, o is 1, and L is a leaving group.
  • m, p, q, and x are 0; (Z) n is a straight-chain or branched aliphatic group having between 1 and 6 carbon atoms, o is 1, and L is a leaving group. In further examples, m, p, q, and x are 0; (Z) n is a straight-chain alkyl group having between 1 and 6 carbon atoms, o is 1, and L is a leaving group. In further examples, m, p, q, and x are 0; (Z) n is a straight-chain alkyl group having between 1 and 4 carbon atoms, o is 1, and L is a leaving group.
  • m, p, q, and x are 0; Z is an aliphatic group having between 1 and 6 carbon atoms; and L is a halide or -OH group.
  • n, q, and w are 1; o is 0, x is 1; A comprises a moiety which terminates in a group selected from H or -CH 3 ; and Z comprises an aliphatic group having at least three carbon atoms.
  • n, q, and w are 1; o is 0, x is 1; A comprises a moiety which terminates in an alkyne group; and Z comprises an aliphatic group having at least three carbon atoms.
  • n, q, and w are 1; o is 0, x is 1; and where the compounds of Formula (IV) comprise at least two different groups, wherein a first subset of groups comprise vinyl styrene moieties, and wherein a second subset of groups comprise allyl moieties.
  • n, q, and w are 1; o is 0, x is 1; and where the compounds of Formula (IV) comprise at least two different groups, wherein a first subset of groups comprise vinyl styrene moieties, and wherein a second subset of groups comprise allyl moieties.
  • the compounds of Formula (IA) or (IB) have the structure defined by Formulas (VA) or (VB): wherein
  • p is an integer ranging from between 1 and 20, and B is X(A) s .
  • p is an integer ranging from between 1 and 20, A is hydrogen, and X is cyclopentadiene or derived from cyclopentadiene.
  • p is an integer ranging from between 1 and 20, A is hydrogen, X is cyclopentadiene or derived from cyclopentadiene, and (Z) n is a straight-chain or branched aliphatic group having between 1 and 6 carbon atoms.
  • p is an integer ranging from between 1 and 20, X is cyclopentadiene substituted with one (A) moiety that is other than hydrogen, and B is X(A) 1 . In some examples, p is an integer ranging from between 1 and 20, X is cyclopentadiene substituted with one (A) moiety that is other than hydrogen, B is X(A) 1 , and (Z) n is a straight-chain or branched aliphatic group having between 1 and 6 carbon atoms.
  • the compounds of Formula (IA) or (IB) have the structure defined by Formula (VI): wherein
  • n is a bond.
  • m is 2 and where each A group is different.
  • X is cyclopentadiene
  • B is H
  • (Z) n is a bond
  • m is an integer ranging from 1 to 5
  • A is a moiety having the structure defined by Formula (IID) of claim 1.
  • A is hydrogen, and X and B are both cyclopentadiene or derived from cyclopentadiene. In other examples, A is hydrogen, X and B are both cyclopentadiene or derived from cyclopentadiene, and (Z) n is a straight-chain or branched aliphatic group having between 1 and 6 carbon atoms. In yet other examples, X is cyclopentadiene substituted with one (A) moiety that is other than hydrogen, and B is X(A) 1 .
  • X is cyclopentadiene substituted with one (A) moiety that is other than hydrogen
  • B is X(A) 1
  • (Z) n is a straight-chain or branched aliphatic group having between 1 and 6 carbon atoms.
  • the compounds of Formula (VI) have the structure defined by Formula (VII): wherein each A is independently H, F, or a saturated or unsaturated, straight-chain or branched, linear or cyclic, substituted or unsubstituted, aliphatic or aromatic group having between 1 and 40 carbon atoms, and which may optionally comprise one or more heteroatoms;
  • the compounds of Formula (IVA) have the structure defined by Formula (VIII): wherein
  • each of the non-limiting examples of resins set forth below have a dielectric value (Dk) of the resin ranges from about 1.5 to about 3.
  • each of the non-limiting examples of resins set forth below have a dissipation value (Df) of the resin ranges from about 0.0001 to about 0.004. In some examples, each of the non-limiting examples of resins set forth below have a glass transition temperature (Tg) of greater than 100°C. In some examples, each of the non-limiting examples of resins set forth below have a glass transition temperature (Tg) of at least 150°C.
  • Df dissipation value
  • Tg glass transition temperature
  • Tg glass transition temperature
  • Tg glass transition temperature
  • each of the non-limiting resins recited below may be included within a kit and/or may be supplied in a suitable solvent. where w and p are independently an integer ranging from 1 to 150, where w and p are each independently an integer ranging from 1 to 150.
  • cyclopentadiene, a cyclopentadiene derivative, a moiety comprising a cyclopentadiene group, or a moiety comprising a cyclopentadiene derivative is provided as a starting material which, in the presence of a base (e.g. NaH), may be converted to the respective anion.
  • a base e.g. NaH
  • Suitable bases may also include hydroxides and alkoxides, if suitable reaction conditions, catalysts, and equipment (such as in a phase-transfer process) are used in such a way as to allow for formation of the cyclopentadiene anion.
  • R a and R b are independently selected from H, F, a C 1 to C 10 linear or cyclic, saturated or unsaturated, branched or straight chain aromatic or aliphatic group
  • T is -CH 2 -, - phenyl,
  • a cyclopentadiene anion is generated by combination of a compound including a cyclopentadiene group with an excess of a strong base, e.g. sodium hydride, in a suitable solvent (e.g. THF) at moderate temperatures (typically between about 0°C and about 100°C).
  • a strong base e.g. sodium hydride
  • THF a suitable solvent
  • This cyclopentadiene anion solution can then be combined with desired molar equivalents of one or more starting materials of Formulas (IXA), (IXB), (IXC), (XA), (XB), and (XC) and allowed to react at moderate temperature for about 30 minutes or until satisfactory conversion to product is achieved.
  • Unreacted base can be neutralized or diluted by addition of water, alcohol or acidic aqueous solution.
  • Crude product mixtures may be isolated by in vacuo removal of reaction solvent. Higher purity product mixtures may be achieved through combinations of dilution in hydrocarbon solvents, filtration of insoluble reaction byproducts, washings with neutral or acidic aqueous solutions to remove reaction byproducts, and removal of solvent in vacuo to produce high yields of resins of Formulas (IA) or (IB).
  • a combination of a compound including a cyclopentadiene; the desired molar equivalents of one or more starting materials of Formulas (IXA), (IXB), (IXC), (XA), (XB), and (XC); and a tetra-alkyl ammonium chloride phase-transfer catalyst are mixed with a strong aqueous base solution (such as about 50 weight% potassium hydroxide in water), and stirred vigorously until product formation is complete.
  • a strong aqueous base solution such as about 50 weight% potassium hydroxide in water
  • This biphasic reaction mixture generates cyclopentadiene anion in the presence of the reactive starting materials, yielding desired product.
  • Product may be isolated by separation of the organic layer, followed by washings with neutral or acidic aqueous solutions to remove reaction byproducts and catalyst to give high yields of resin of Formula (IA) or (IB).
  • a compound including a cyclopentadiene group may first be treated with a base and subsequently reacted with a compound of any of Formulas (IXA), (IXB), or (IXC) to provide a resin of Formulas (IA) or (IB).
  • a compound including a cyclopentadiene group may first be treated with a base and subsequently reacted with a compound of any of Formulas (XA), (XB), and (XC) to provide a resin of Formula (IA) or (IB):
  • the starting materials of Formulas (IXA), (IXB), (IXC), (XA), (XB), and (XC) and cyclopentadiene or a derivative thereof may be combined in any order to generate a thermosetting resin formulation meeting desired characteristics.
  • Preparation of the anion of cyclopentadiene or a derivative thereof can be completed before reaction with a compound of any of Formulas (IXA), (IXB), (IXC), (XA), (XB), and (XC) and any additional reactive compounds.
  • the anion of cyclopentadiene or a derivative thereof can be generated in the presence of a compound of any of Formulas (IXA), (IXB), (IXC), (XA), (XB), and (XC) and any additional reactive compounds such that the anion reacts quickly after formation.
  • reaction product is formed having Formula (IA) or (IB).
  • the generated resin of Formulas (IA) or (IB) serving as an intermediate may become further deprotonated, regenerating a stable anion capable of further reaction with additional compounds of any of Formulas (IXA), (IXB), (IXC), (XA), (XB), and (XC) to form yet a different product having any of Formula (IA) or (IB).
  • reaction components can be combined in various ways to affect the overall product distribution, as understood by those skilled in the art. If desired, one or more of the reactive components of the disclosure can be formed in situ during the reaction process.
  • the viscosity of the thermosetting resin formulation can be tuned as desired by moderation of the molar ratios of the reactive components and molar equivalents of base. Increasing the base-to-cyclopentadiene or a derivative thereof molar ratio promotes multiple reactions between the cyclopentadiene or a derivative thereof and other reactive components, when the specific structure of the cyclopentadiene or a derivative thereof is capable of more than one formation of the reactive anion and the viscosity of the product composition typically increases with an increase in the average number of reactions per cyclopentadiene or a derivative thereof.
  • a cyclopentadiene or a derivative thereof is reacted with 2 or more equivalents of a compound of any of Formulas (IXA), (IXB), (IXC), (XA), (XB), and (XC) in the presence of 2 or more equivalents of strong base to form a product composition featuring 2 or more moieties capable of carbon-carbon bond forming reactions per cyclopentadiene or a derivative unit.
  • Reaction compounds may be combined at any temperature suitable to effect formation of an appropriate resin formulation.
  • Reaction of cyclopentadiene or a derivative thereof with strong base is typically performed at temperatures from about -70°C to about 200°C, with optimal reaction temperatures depending heavily on properties of solvent and equipment used in the chemistry. In some examples, the reaction is conducted at temperatures between about 20°C to about 100°C.
  • the reaction may be conducted in any suitable solvent, including ethers (tetrahydrofuran, diglyme) and hydrocarbon solvents (xylene, toluene).
  • the reaction may also be conducted in the absence of solvent, if reaction components are sufficiently miscible to generate desired products.
  • Reactions may be conducted in biphasic systems of aqueous base and organic reactants, with and without additional organic solvents, and with or without added phase-transfer catalysts such as tetra-substituted ammonium salts.
  • Product mixtures may be isolated by filtration of solid reaction byproducts (salts), solvent extractions to remove aqueous-soluble material, and removal of solvent by evaporation, distillation, or vacuum distillation.
  • dienophile refers to an alkene that is reactive toward a diene to provide a 4+2 cycloaddition product.
  • Dienophiles useful in the present methods and composition include, but are not limited to, carbon-containing dienophiles (e.g.
  • the dienophile is an alkene such as ethylene, propylene or other straight chain alkene (e.g. an acrylate), or a cyclic alkene (e.g. cyclopentadiene), as described herein.
  • the dienophile is a bis-maleimide.
  • bis-maleimide as used herein includes mono-, bis-, tris-, tetrakis-, and higher functional maleimides and their mixtures.
  • bis-maleimide resins may be prepared by the reaction of maleic anhydride or a substituted maleic anhydride such as methylmaleic anhydride, with an aromatic or aliphatic di- or polyamine.
  • suitable bis-maleimides include, but are not limited to: 1,6'-bismaleimide-(2,2,4-trimethyl)hexane ( CAS 39979-46-9 ), BMI-3000 (a imide-extended BMI oligomer, available from Designer Molecules Inc.), BMI-689 (bismaleimide of dimer diamine, CAS-No. 682800-79-9 ), 4,4'-Diphenylmethanebismaleimide ( CAS-No. 13676-54-5 ), Polyphenylmethanebismaleimide ( CAS-No. 28630-26-4 ), N,N'-(4-methyl-m-phenylene)-bismaleimide ( CAS-No.
  • N,N'-m-phenylenebismaleimide (CAS-No. 3006-93-7 ), Prepolymer bismaleimide resins (e.g. Hos-Technik Homide 250 available as CAS-No. 26140-67-0 ), bisphenol A diphenyl ether bismaleimide ( CAS-No. 79922-55-7 ), 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, ( CAS-No. 105391-33-1 ), N,N'-[Methylenebis(2,6-diethyl-4,l-phenylene)]bis(maleimide) ( CAS-No.
  • suitable bis-maleimides have the structure depicted by the following examples: where the R functional groups are independently selected from hydrogen, aromatics, substituted aromatics, aliphatics, substituted aliphatics, cyclo-aliphatics, and substituted cyclo-aliphatics.
  • suitable dienophiles include, but are not limited to, maleic anhydride, derivatives of maleic anhydride, benzoquinone, and derivatives of benzoquinone.
  • suitable benzoquinone derivatives include 1,4-benzoquinone, 2-methylbenzoquinone, 2,3-dimethylbenzoquinone, 2,5-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3,5-trimethylbenzoquinone, 2,3,5,6-tetramethylbenzoquinone, and the like and combinations thereof.
  • maleic derivatives include, but are not limited to, maleic anhydride, methyl maleic anhydride, dimethyl maleic anhydride, maleimide, N-methyl maleimide, N-ethyl maleimide, methyl maleimide, dimethyl maleimide, methyl-N-methyl maleimide, dimethyl-N-methyl maleimide, and the like and combinations thereof.
  • the dienophile is a bis-acrylate or an acrylate. In other examples, the dienophile is a dialkyl fumarate, a dialkyl maleate, a dialkylacetylenedicarboxylate. In some examples, the dienophile is selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, vinyl acrylate, dimethyl fumarate, dimethyl maleate, diethyl fumarate, diethyl maleate, diphenyl fumarate, divinyl fumarate, divinylmaleate, acrolein, methyl vinyl ketone, divinylketone, acrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide, N,N-diethyl acrylamide, N,N-diethyl acrylamide, acrylonitrile, methacrylonitrile, 1,1-dicyanoethylene
  • acrylates include hexane diol diacrylate and other C 4 -C 10 alkane diacrylates, bisphenol A diacrylate, pentaerythritol tetraacrylate, propylene glycol diacrylate, ethylene glycol diacrylate, trimethylol propane triacrylate, cyclohexane dimethanol diacrylate, tricyclodecane dimethanol diacrylate, neopentyl glycol diacrylate, tris(2-hydroxyethyl) isocyanurate triacrylate, and polybutadiene diacrylate, or the ethoxylated or propoxylated derivatives thereof.
  • acrylates include hexane diol di(meth)acrylate and other C 4 -C 10 alkane di(meth)acrylates, bisphenol A di(meth)acrylate, pentaerythritol tetra(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylol propane tri(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, tricyclodecane dimethanol d(meth)acrylate, neopentyl glycol di(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, and polybutadiene di(meth)acrylate, or the ethoxylated or propoxylated derivatives thereof.
  • the present disclosure provides for a reaction product between (i) a resin having one of the following structures: and where w and p each are independently an integer ranging from 1 to 150; and (ii) a dienophile, wherein the dienophile is selected from the group consisting of a bis-maleimide, a derivative of a bis-maleimide, a maleic anhydride, a derivative of a maleic anhydride, a benzoquinone, a derivative of a benzoquinone, and an acrylate.
  • a composition comprising at least two of the reaction products described above.
  • a ratio of a first reaction product to a second reaction product ranges from about 1:10 to about 10:1. In some examples, the ratio ranges from about 1:5 to about 5:1. In some examples, the ratio ranges from about 1:2 to about 2:1.
  • reaction products between a compound of any of Formulas (IA) or (IB) and a dienophile have the structure set forth in Formulas (XIA) and (XIB): wherein
  • R 9 or R 10 is a straight chain or branched, linear or cyclic, alkyl group having between 1 and 20 carbon atoms, which may be optionally substituted with one or more heteroatoms (e.g. O, N, or S).
  • R 9 or R 10 is a moiety having between 1 and 20 carbon atoms and having at least one aromatic or heteroaromatic group, and where the aromatic or heteroaromatic groups may be substituted or unsubstituted.
  • one of R 9 or R 10 may be -phenyl-[C 1 -C 4 alkyl group]-phenyl-.
  • R 10 comprises -[Aryl]-[Alkyl]-[Aryl], where each aryl group may be independently substituted or unsubstituted, and where the alkyl group comprises between 1 and 20 carbon atoms.
  • each [Aryl] group is optionally substituted with a C 1 -C 10 straight chain or branched alkyl group.
  • R 10 has the structure defined by Formula (XIVa): wherein each alkyl group is independently straight chain or branched and comprises between 1 and 10 carbon atoms; and where each h is independently 0 or an integer ranging from 1 to 4. In some examples, each alkyl group independently comprises between 1 and 6 carbon atoms. In some examples, each alkyl group independently comprises between 1 and 4 carbon atoms. In some examples, each alkyl group independently comprises between 1 or 2 carbon atoms.
  • Formula (XIVa) wherein each alkyl group is independently straight chain or branched and comprises between 1 and 10 carbon atoms; and where each h is independently 0 or an integer ranging from 1 to 4. In some examples, each alkyl group independently comprises between 1 and 6 carbon atoms. In some examples, each alkyl group independently comprises between 1 and 4 carbon atoms. In some examples, each alkyl group independently comprises between 1 or 2 carbon atoms.
  • At least one (Alkyl) h group is -CH 3 . In some examples, at least one (Alkyl) h group is -CH 2 -CH 3 . In some examples, at least one (Alkyl) h group is -C(H)(CH 3 ) 2 .
  • each (Alkyl) h group is -CH 2 -CH 3 .
  • each aryl group comprises two (Alkyl) h groups, and each (Alkyl) h group is -CH 2 -CH 3 .
  • each aryl group comprises two (Alkyl) h groups, where a first (Alkyl) h group is -CH 3 and another (Alkyl) h group is -C(H)(CH 3 ) 2 .
  • R 10 has the structure wherein the alkyl group is a straight chain or branched and comprises between 1 and 10 carbon atoms. In some examples, the alkyl group comprises between 1 and 4 carbon atoms. In some examples, the alkyl group is -CH 2 -.
  • R 10 is a branched alkyl group comprising between 1 and 12 carbon atoms. In some examples, R 10 is a branched alkyl group comprising between 1 and 10 carbon atoms. In some examples, R 10 is a branched alkyl group comprising between 1 and 9 carbon atoms. In some examples, R 10 is -CH 2 -C(CH 3 ) 2 -CH 2 -CH(CH 3 )-CH 2 -CH 2 -.
  • R 10 is a 6-membered aromatic ring, optionally substituted with up to four alkyl groups.
  • R 10 is a six-membered cycloalkyl group, optionally substituted with up to four alkyl groups.
  • R 10 is -[Alkyl]-[Cycloalkyl]-[Alkyl]-, where each alkyl group is linear or branched and comprises from 1 to 10 carbon atoms; and where the cycloalkyl group comprises between 4 and 8 carbon atoms, the cycloalkyl group being optionally substituted with one or more straight chain or branched alkyl groups, each having between 1 and 10 carbon atoms.
  • reaction products between a compound of any of Formulas (IA) or (IB) and a dienophile have the structure set forth in Formulas (XID) and (XIE): wherein
  • reaction products between a compound of any of Formulas (IA) or (IB) and a dienophile have the structure set forth in Formulas (XIF) and (XIG): wherein
  • each R 9 is independently selected from -O-alkyl. In some examples, each R 9 is independently selected from -O-(C 1 -C 20 )-. In some examples, each R 9 is independently selected from -O-(C 1 -C 10 ). In some examples, each R 9 is independently selected from -O-(C 1 -C 6 ). In some examples, each R 9 is independently selected from -O-(C 1 -C 4 ). In some examples, each R 9 is independently selected from -O-(C 1 -C 3 ).
  • reaction products between a compound of any of Formulas (IA) or (IB) and a dienophile have the structure set forth in Formulas (XIIA) or (XIIB): wherein
  • R 14 comprises -[Aryl]-[Alkyl]-[Aryl]-, where each aryl group may be independently substituted or unsubstituted, and where the alkyl group comprises between 1 and 20 carbon atoms.
  • each [Aryl] group is optionally substituted with a C 1 -C 10 straight chain or branched alkyl group.
  • R 14 has the structure defined by Formula (XIVa): wherein each alkyl group is independently straight chain or branched and comprises between 1 and 10 carbon atoms; and where each h is independently 0 or an integer ranging from 1 to 4. In some examples, each alkyl group independently comprises between 1 and 6 carbon atoms. In some examples, each alkyl group independently comprises between 1 and 4 carbon atoms. In some examples, each alkyl group independently comprises between 1 or 2 carbon atoms.
  • Formula (XIVa) wherein each alkyl group is independently straight chain or branched and comprises between 1 and 10 carbon atoms; and where each h is independently 0 or an integer ranging from 1 to 4. In some examples, each alkyl group independently comprises between 1 and 6 carbon atoms. In some examples, each alkyl group independently comprises between 1 and 4 carbon atoms. In some examples, each alkyl group independently comprises between 1 or 2 carbon atoms.
  • At least one (Alkyl) h group is -CH 3 . In some examples, at least one (Alkyl) h group is -CH 2 -CH 3 . In some examples, at least one (Alkyl) h group is -C(H)(CH 3 ) 2 .
  • each (Alkyl) h group is -CH 2 -CH 3 .
  • each aryl group comprises two (Alkyl) h groups, and each (Alkyl) h group is -CH 2 -CH 3 .
  • each aryl group comprises two (Alkyl) h groups, where a first (Alkyl) h group is -CH 3 and another (Alkyl) h group is -C(H)(CH 3 ) 2 .
  • R 14 has the structure wherein the alkyl group is a straight chain or branched and comprises between 1 and 10 carbon atoms. In some examples, the alkyl group comprises between 1 and 4 carbon atoms. In some examples, the alkyl group is -CH 2 -.
  • R 14 is a branched alkyl group comprising between 1 and 12 carbon atoms. In some examples, R 14 is a branched alkyl group comprising between 1 and 10 carbon atoms. In some examples, R 14 is a branched alkyl group comprising between 1 and 9 carbon atoms. In some examples, R 14 is - CH 2 -C(CH 3 ) 2 -CH 2 -CH(CH 3 )-CH 2 -CH 2 -.
  • R 14 is a six-membered cycloalkyl group, optionally substituted with up to four alkyl groups. In some examples, R 14 is a six-membered cycloalkyl group, optionally substituted with up to four -CH 3 groups. In some examples, R 14 is a six-membered cycloalkyl group, optionally substituted with up to two -CH 3 groups.
  • R 14 is a six-membered cycloalkyl group, optionally substituted with up to four alkyl groups.
  • R 14 is -[Alkyl]-[Cycloalkyl]-[Alkyl]-, where each alkyl group is linear or branched and comprises from 1 to 10 carbon atoms; and where the cycloalkyl group comprises between 4 and 8 carbon atoms, the cycloalkyl group being optionally substituted with one or more straight chain or branched alkyl groups, each having between 1 and 10 carbon atoms.
  • composition comprising a blend of one or more compounds of any of Formulas (XIIA) or (XIIB).
  • a ratio of a first compound of any of Formulas (XIIA) or (XIIB) to a second compound of any of any of Formulas (XIIA) or (XIIB) ranges from about 1:10 to about 10:1. In some examples, the ratio ranges from about 1:5 to about 5:1. In some examples, the ratio ranges from about 1:2 to about 2:1.
  • reaction products between a compound of any of Formulas (IA) or (IB) and a dienophile have the structure set forth in Formulas (XIIC) or (XIID): wherein
  • R 14 is comprises -[Aryl]-[Alkyl]-[Aryl]-, where each aryl group may be independently substituted or unsubstituted, and where the alkyl group comprises between 1 and 20 carbon atoms.
  • each [Aryl] group is optionally substituted with a C 1 -C 10 straight chain or branched alkyl group.
  • R 14 has the structure defined by Formula (XIVa): wherein each alkyl group is independently straight chain or branched and comprises between 1 and 10 carbon atoms; and where each h is independently 0 or an integer ranging from 1 to 4. In some examples, each alkyl group independently comprises between 1 and 6 carbon atoms. In some examples, each alkyl group independently comprises between 1 and 4 carbon atoms. In some examples, each alkyl group independently comprises between 1 or 2 carbon atoms.
  • Formula (XIVa) wherein each alkyl group is independently straight chain or branched and comprises between 1 and 10 carbon atoms; and where each h is independently 0 or an integer ranging from 1 to 4. In some examples, each alkyl group independently comprises between 1 and 6 carbon atoms. In some examples, each alkyl group independently comprises between 1 and 4 carbon atoms. In some examples, each alkyl group independently comprises between 1 or 2 carbon atoms.
  • At least one (Alkyl) h group is -CH 3 . In some examples, at least one (Alkyl) h group is -CH 2 -CH 3 -. In some examples, at least one (Alkyl) h group is -C(H)(CH 3 ) 2 .
  • each (Alkyl) h group is -CH 2 -CH 3 .
  • each aryl group comprises two (Alkyl) h groups, and each (Alkyl) h group is -CH 2 -CH 3 .
  • each aryl group comprises two (Alkyl) h groups, where a first (Alkyl) h group is -CH 3 and another (Alkyl) h group is -C(H)(CH 3 ) 2 .
  • R 14 has the structure wherein the alkyl group is a straight chain or branched and comprises between 1 and 10 carbon atoms. In some examples, the alkyl group comprises between 1 and 4 carbon atoms. In some examples, the alkyl group is -CH 2 -.
  • R 14 is a branched alkyl group comprising between 1 and 12 carbon atoms. In some examples, R 14 is a branched alkyl group comprising between 1 and 10 carbon atoms. In some examples, R 14 is a branched alkyl group comprising between 1 and 9 carbon atoms. In some examples, R 14 is - CH 2 -C(CH 3 ) 2 -CH 2 -CH(CH 3 )-CH 2 -CH 2 -.
  • R 14 is a six-membered cycloalkyl group, optionally substituted with up to four alkyl groups. In some examples, R 14 is a six-membered cycloalkyl group, optionally substituted with up to four -CH 3 groups. In some examples, R 14 is a six-membered cycloalkyl group, optionally substituted with up to two -CH 3 groups.
  • R 14 is a six-membered cycloalkyl group, optionally substituted with up to four alkyl groups.
  • R 14 is -[Alkyl]-[Cycloalkyl]-[Alkyl]-, where each alkyl group is linear or branched and comprises from 1 to 10 carbon atoms; and where the cycloalkyl group comprises between 4 and 8 carbon atoms, the cycloalkyl group being optionally substituted with one or more straight chain or branched alkyl groups, each having between 1 and 10 carbon atoms.
  • reaction products between a compound of any of Formulas (IA) or (IB) and a dienophile have the structure set forth in Formula (XIIE): wherein
  • R 14 is comprises -[Aryl]-[Alkyl]-[Aryl]-, where each aryl group may be independently substituted or unsubstituted, and where the alkyl group comprises between 1 and 20 carbon atoms.
  • each [Aryl] group is optionally substituted with a C 1 -C 10 straight chain or branched alkyl group.
  • R 14 has the structure defined by Formula (XIVa): wherein each alkyl group is independently straight chain or branched and comprises between 1 and 10 carbon atoms; and where each h is independently 0 or an integer ranging from 1 to 4. In some examples, each alkyl group independently comprises between 1 and 6 carbon atoms. In some examples, each alkyl group independently comprises between 1 and 4 carbon atoms. In some examples, each alkyl group independently comprises between 1 or 2 carbon atoms. In some examples, at least one (Alkyl) h group is -CH 3 . In some examples, at least one (Alkyl) h group is -CH 2 -CH 3 .
  • At least one (Alkyl) h group is -C(H)(CH 3 ) 2 .
  • each (Alkyl) h group is -CH 2 -CH 3 .
  • each aryl group comprises two (Alkyl) h groups, and each (Alkyl) h group is -CH 2 -CH 3 .
  • each aryl group comprises two (Alkyl) h groups, where a first (Alkyl) h group is -CH 3 and another (Alkyl) h group is -C(H)(CH 3 ) 2 .
  • R 14 has the structure wherein the alkyl group is a straight chain or branched and comprises between 1 and 10 carbon atoms. In some examples, the alkyl group comprises between 1 and 4 carbon atoms. In some examples, the alkyl group is -CH 2 -.
  • R 14 is a branched alkyl group comprising between 1 and 12 carbon atoms. In some examples, R 14 is a branched alkyl group comprising between 1 and 10 carbon atoms. In some examples, R 14 is a branched alkyl group comprising between 1 and 9 carbon atoms. In some examples, R 14 is - CH 2 -C(CH 3 ) 2 -CH 2 -CH(CH 3 )-CH 2 -CH 2 -.
  • R 14 is a 6-membered aromatic ring, optionally substituted with up to four alkyl groups.
  • R 14 is a six-membered cycloalkyl group, optionally substituted with up to four alkyl groups. In some examples, R 14 is a six-membered cycloalkyl group, optionally substituted with up to four -CH 3 groups. In some examples, R 14 is a six-membered cycloalkyl group, optionally substituted with up to two -CH 3 groups.
  • R 14 is -[Alkyl]-[Cycloalkyl]-[Alkyl]-, where each alkyl group is linear or branched and comprises from 1 to 10 carbon atoms; and where the cycloalkyl group comprises between 4 and 8 carbon atoms, the cycloalkyl group being optionally substituted with one or more straight chain or branched alkyl groups, each having between 1 and 10 carbon atoms.
  • R 14 is -[Aryl]-(R 13 ) k -[Aryl]-, where each aryl group may be independently substituted or unsubstituted.
  • each -[Aryl]- group is optionally substituted with a C 1 -C 10 straight chain or branched alkyl group.
  • each -[Aryl]-group is unsubstituted.
  • R 14 is -[alkyl]-(R 13 ) k -, where the alkyl group may comprises between 1 and 40 carbon atoms. In some examples, R 14 is -[alkyl]-[cycloalkyl]-[alkyl]-(R 13 ) k -, the cycloalkyl group comprising between 4 and 8 carbon atoms, the cycloalkyl group being optionally substituted with one or more straight chain or branched alkyl groups, each having between 1 and 10 carbon atoms.
  • R 13 comprises a moiety including a substituted phenyl group.
  • reaction products between a compound of any of Formulas (IA) or (IB) and a dienophile have the structure set forth in Formula (XIIF): wherein
  • each R 16 is independently H or a C 1 - C 4 alkyl group.
  • reaction products between a compound of any of Formulas (IA) or (IB) and a dienophile have the structure set forth in Formula (XIII): wherein
  • one of w or p is 0. In other examples, w and p are both 0.
  • reaction products of a resin of any of Formulas (IA) or (IB) and a dienophile are illustrated within the synthetic examples herein.
  • the compounds of Formulas (XIA), (XIB), (XID) to (XIG), (XIIA) to (XIIF), and (XIII) may be prepared by neat blending combination of resins of Formulas (IA) or (IB) with one or more suitable dienophiles, including those described herein.
  • compounds of Formulas (XIA), (XIB), (XID) to (XIG), (XIIA) to (XIIF), and (XIII) may be prepared by combination of resins of Formula (IA) or (IB) with one or more suitable dienophiles in an organic solvent at moderate temperatures (typically between 0°C and 100°C).
  • Reactions between resins of Formulas (IA) or (IB) and suitable dienophiles are typically rapid and self-initiating, and compounds of Formulas (XIA), (XIB), (XID) to (XIG), (XIIA) to (XIIF), and (XIII) can be used as-generated, or purified by removal of reaction solvent in vacuo as desired.
  • an excess of diene is used compared to an amount of dienophile.
  • a ratio of an amount of diene to dienophile ranges from about 1:1 to about 1:4. In other examples, a ratio of an amount of diene to dienophile ranges from about 1:1 to about 1:2.
  • the compounds of Formulas (XIA), (XIB), (XID) to (XIG), (XIIA) to (XIIF), and (XIII) may be prepared according to the methods outlined in the following non-limiting synthetic schemes:
  • R is R 14 as defined herein.
  • n is an integer ranging from 1 to 10.
  • n is an integer ranging from 1 to 10.
  • a polymer is provided, the polymer being derived from one or more resins of Formulas (IA) or (IB) (or any like resin disclosed herein).
  • the polymer further comprises an additive selected from the group consisting of adhesion agents, peroxides/crosslinking agents, antioxidants, flame retardants, diluents and fillers.
  • a co-polymer is provided, the co-polymer derived from a first resin of Formulas (IA) or (IB)and a second resin of Formulas (IA) or (IB), wherein the first and second resins are different.
  • an interpenetrating polymer network is provided, the interpenetrating polymer network derived from a first resin of Formulas (IA) or (IB)and a second resin of Formulas (IA) or (IB), wherein the first and second resins are different.
  • a co-polymer or an interpenetrating polymer network is provided, the co-polymer or the interpenetrating polymer network being derived from a resin of Formulas (IA) or (IB), and a second component that differs from the resin of Formulas (IA) or (IB).
  • the second component is selected from the group consisting of polyethylenes, polypropylenes, polybutylenes, low vinyl polybutadienes (predominantly 1,3 addition), high vinyl polybutadienes (significant 1,2 addition), polystyrenes, butadiene-styrene copolymers, SMA polymers, ABS polymers, polydicyclopentadienes, epoxies, polyurethanes, cyanate esters, poly(phenylene oxide), EPDM polymers, cyclic olefin copolymers (COC), polyimides, bismaleimides, phosphazenes, olefin-modified phosphazenes, acrylates, vinyl esters, polylactones, polycarbonates, polysulfones, polythioethers, polyetheretherketones (PEEK), polydimethylsiloxanes (PDMS), polyethylene terephthalates (PET), polybutylene terephthal
  • the second component is selected from the group consisting of styrene, divinylbenzene, 1,2-bis(vinylphenyl)ethane, vinylbenzyl ether compounds, vinyl ether compounds, allyl ether compounds, vinylphenyl monomers, vinyl monomers, allyl monomers, or derivatives of such components.
  • Suitable components include, but are not limited to, vinyl-functionalized cyanate ester HTL-300 (available from Lonza Chemicals), low- and high-vinyl Ricon polybutadienes (Total/Cray Valley), butadiene-styrene Ricon copolymers (Total/Cray Valley), Sartomer acrylate monomers (Arkema), olefin-containing phosphazene SPV-100 (Otsuka Chemicals), bismaleimide BMPI-300 (Lonza Chemicals), bismaleimide Cycom 5250 (Cytec Solvay), bismaleimide BMI-1700 (Designer Molecules Inc.), bismaleimide BMI-3000 (Designer Molecules, Inc.), bismaleimide BMI-689 (Designer Molecules, Inc.), bismaleimide Homide 250 (HOS-Technik GmbH), bismaleimide BMI-2300 (Daiwakaskei Industry Co., LTD), bismaleimide
  • Resin compositions of the present disclosure can be used as-isolated, or in blends with other copolymers, adhesion agents, peroxides/crosslinking agents, antioxidants, flame retardants, diluents and other additives or fillers known in the art.
  • the resins disclosed herein may be blended with other polymers.
  • Such other polymers may be reactive such that they are copolymerized with the resin compositions of the present disclosure to form random or block copolymers.
  • Alternately such other polymers may be formed by alternate means such that an interpenetrating polymer network or polymer phase dispersion is formed.
  • Such other polymers include but are not limited to polyethylenes, polypropylenes, polybutylenes, low vinyl polybutadienes (predominantly 1,3 addition), high vinyl polybutadienes (significant 1,2 addition), polystyrenes, butadiene-styrene copolymers, SMA polymers (styrene maleic anhydride polymers), ABS polymers (acrylonitrile butadiene styrene polymers), polydicyclopentadienes, epoxies, polyurethanes, cyanate esters, poly(phenylene oxide), EPDM polymers (polymers derived from ethylene propylene diene monomers), cyclic olefin copolymers (COC), polyimides, bismaleimides, phosphazenes, olefin-modified phosphazenes, acrylates, vinyl esters, polylactones, polycarbonates, polysulfones, polythioethers,
  • the resins disclosed herein may be blended with an electrical property modifier.
  • the electrical property modifier may include cyanate ester derived compounds and bismaleimide triazine copolymers.
  • a cyanate ester derived compound broadly refers to a chemical substance generally based on a bisphenol or novolac derivative, in which the hydrogen atom of at least one hydroxyl group of the bisphenol or novolac derivative is substituted by a cyanide group. Therefore, a cyanate ester derived compound generally has an -OCN group.
  • a cyanate ester derived compound may refer to, without limitation, 4,4 ' -ethylidenebisphenylene cyanate, 4,4' -dicyanatodiphenyl, 2,2-bis(4-cyanatophenyl)propane, bis(4-cyanato-3,5-dimethylphenyl)methane, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)ether, prepolymer of bisphenol A dicyanate in methyl ethyl ketone, 1,1-bis(4-cyanatophenyl)ethane, 1,1-bis(4-cyanatophenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)-2,2-butane, 1,3-bis[2-(4-cyanato phen
  • Resins of the present disclosure may be blended with various additives and adhesion agents to improve resin adhesion and compatibility with reinforcement substrates such as glass, carbon or aramid fibers.
  • Suitable adhesion promoting additives include but are not limited to maleic anhydride, styrene maleic anhydrides, functionalized trialkoxysilanes, maleic anhydride-grafted polyolefins, as well as other polymers previously detailed in this disclosure which are capable of improved substrate adhesion.
  • Resin compositions of the present disclosure may be cured into a solid material by self-polymerization reactions at elevated temperatures, or by action of added radical initiators.
  • Suitable radical initiators include but are not limited to dialkyl peroxides, diacyl peroxides, and azo compounds.
  • Particularly suitable radical initiators include dicumyl peroxide and 2,5-Dimethyl-2,5-di-(tert-butylperoxy)hexyne-3 (Trigonox 145-E85).
  • Radical initiators may be added at any level suitable to effect sufficient polymerization, ranging from ppm levels to 3wt% depending on initiator used. If a radical initiator is used, it may be used in an amount ranging from about 0.5% to about 1.5% by weight of the composition.
  • Resin compositions of the present disclosure can be cured into a solid material at temperatures ranging from between about 120°C to about 200°C for between about 30 minutes and about 240 minutes. In some examples, the resin compositions may be cured into a solid material at temperatures ranging from between about 150°C to about 175°C for between about 60 minutes and about 180 minutes. The resin can then optionally be heated to higher temperatures for additional polymer curing as desired. In some examples, the resins of this disclosure, when fully cured, generate solid thermoset materials that possess glass transition temperatures (Tg) greater than 100°C. In some examples, the resins of this disclosure, when fully cured, generate solid thermoset materials that possess glass transition temperatures (Tg) greater than 150°C.
  • the resins of this disclosure when fully cured, generate solid thermoset materials that possess glass transition temperatures (Tg) greater than 200°C. In some examples, the resins of this disclosure, when fully cured, generate solid thermoset materials that possess glass transition temperatures (Tg) ranging from about 100°C to about 400°C. In yet other examples, the resins of this disclosure, when fully cured, generate solid thermoset materials that possess glass transition temperatures (Tg) ranging from about 125°C to about 400°C. In yet other examples, the resins of this disclosure, when fully cured, generate solid thermoset materials that possess glass transition temperatures (Tg) ranging from about 175°C to about 400°C.
  • crosslinking agents include but are not limited to triallyl cyanurate, triallyl isocyanurate, polybutadiene dimethacrylates, polybutadiene diacrylates, divinylbenzene, 1,2-bis(vinylphenyl)ethane, vinylbenzyl ether compounds, vinyl ether compounds, allyl ether compounds, vinylphenyl monomers, vinyl monomers, allyl monomers, and similar compounds containing two or more carbon-carbon bond forming moieties per molecule.
  • Resin compositions of the present disclosure may be blended with solvents prior to polymerization, if desired, for certain applications.
  • Any solvent known by one with skill in the art to be useful in conjunction with resin composition can be used.
  • Particularly useful solvents include methyl ethyl ketone (MEK), xylene, toluene, DMF, and mixtures thereof.
  • the solvents are selected from MEK or toluene.
  • solvents are present in the resin composition in the amount ranging from between about 1% to about 99% by weight of the composition. In other examples, solvents are present in the resin composition in an amount ranging from between about 10% and about 60% by weight of the composition.
  • solvents are present in the resin composition in an amount ranging from between about 15% and about 30% by weight of the composition. In yet other examples, solvents are present in the resin composition in an amount ranging from between about 20% to about 25% by weight of the composition.
  • Such solvent-blended resin compositions of the present disclosure are most useful for production of prepreg-style reinforcement layers.
  • thermosetting resin compositions of the present disclosure may additionally be formulated with other standard antioxidants, flame retardants, fillers, diluents, stabilizers, processing aids and other additives as are commonly used in such applications.
  • additives include, but are not limited to, phenolic antioxidants, dielectric fillers and commercial flame retardants. Most commercial flame retardants are suitable for use with resins of the present disclosure. Suitable flame retardants also include phosphazenes and olefin-modified phosphazenes.
  • resin laminates made from resin composition can be made V0 without halogenated flame retardant using reactive phosphorus flame retardants such as (vinyl or other radical-reactive FR), as well as non-reactive phosphorus flame retardants.
  • thermosetting resin compositions of the subject disclosure may also be used to provide prepregs with and without tack.
  • the compositions are particularly useful in preparation of high Tg laminates having ultra-low dielectric constants and ultra-low dielectric loss. These electrical properties help solve signal speed and signal integrity problems encountered with highspeed analog and digital circuitry applications.
  • the thermosetting resin compositions of the subject disclosure are useful for making prepregs in a continuous process with and without solvent.
  • the viscosity of the inventive compositions can be adjusted for hot/melt prepreg and present substantial cost savings for prepreg production.
  • Prepregs are generally manufactured using a reinforcement material including but not limited to woven glass, carbon, Kevlar, spectra, aramid or quartz fibers.
  • thermosetting resin composition of the present disclosure may also be coated directly to any polymeric film for build-up PCB.
  • Thermosetting resin compositions of the present disclosure may also be directly coated to copper using slot-die or other related coating techniques for resin-coated copper (RCC).
  • RRC resin-coated copper
  • the prepreg materials made from thermosetting resins of the present disclosure can also be converted to laminates.
  • the lamination process typically follows the stack-up of one or more prepreg layers between one or more sheets of conductive foil such as copper foil. This process is often described as copper-clad laminates (CCL) and is generally well-known to persons with ordinary skill in the art. Pressure and temperature applied to the prepreg stack result in the formation of laminates.
  • the laminates produced from the present disclosure exhibit high Tg.
  • compositions of the present disclosure that produce laminates of moderate Tg (>150°C) with considerable flexibility. Flexible laminates are very useful for various bendable electronic devices.
  • Thermosetting resins of the present disclosure with sufficiently low viscosities may also be used for vacuum infusion applications, where reinforcement materials as previously defined are impregnated with resin formulations of the present disclosure by action of vacuum pressure. Resins of the present disclosure with sufficiently low viscosities may be used in solventless or environmentally friendly manufacturing techniques for various applications. Resins of the present disclosure may also be used in 3D printing applications, including continuous liquid interface printing (CLIP) and stereolithography (SLA) applications.
  • CLIP continuous liquid interface printing
  • SLA stereolithography
  • Resins of Formulas (IA) or (IB) may additionally be used as additives, reactive diluents, or copolymers for commercial polymers used in electronic applications, providing improvements in resin viscosity and dielectric properties.
  • resins of Formulas (IA) or (IB) may be combined with resins based on cyanate esters, epoxies, bismaleimides, or polyolefins to generate blends with improved manufacturing properties, mechanical performance, or electrical performance.
  • kits comprising any of the resins, polymers, blends, etc. disclosed herein.
  • the resins, polymers, blends, etc. are mixed with a suitable solvent.
  • the kits comprise multiple resins, polymers, blends, etc., where each of the resins, polymers, blends, etc. are provided in a separate container.
  • the kits include a resin and other reactants, reagents, or solvents.
  • the kits further comprise instructions.
  • a kit may include a resin of any of Formulas (IA) or (IB) and also may include a bis-maleimide, such that the resin and the bis-maleimide may be reacted to form a product.
  • Any bis-maleimides may be included in a kit, including any of those recited herein.
  • the kit includes a bis-maleimide is selected from the group consisting of 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-Diphenylmethanebismaleimide, Polyphenylmethanebismaleimide, N,N'-(4-methyl-m-phenylene)-bismaleimide, N,N'-m-phenylenebismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, N,N'-[Methylenebis(2,6-diethyl-4,1-phenylene)]bis(maleimide, N,N'-[Methylenebis(2-isopropyl-6-methyl-4,1-phenylene)]bis(maleimide), 1,2-bis(maleimido)ethane, 1,4-bis(maleimido)butane, and 1,6-bis(maleimi
  • a kit may include a resin of any of Formulas (IA) or (IB) and also may include a crosslinking agent, such as a crosslinking agent selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, polybutadiene dimethacrylates, polybutadiene diacrylates, divinylbenzene, 1,2-bis(vinylphenyl)ethane, vinylbenzyl ether compounds, vinyl ether compounds, allyl ether compounds, vinylphenyl monomers, vinyl monomers, and allyl monomers.
  • a crosslinking agent such as a crosslinking agent selected from the group consisting of triallyl cyanurate, triallyl isocyanurate, polybutadiene dimethacrylates, polybutadiene diacrylates, divinylbenzene, 1,2-bis(vinylphenyl)ethane, vinylbenzyl ether compounds, vinyl ether compounds, allyl ether compounds, vinylphenyl monomers,
  • the resins, reaction products, blends, polymers, compositions, etc. described herein may be utilized in any suitable application.
  • the resins, reaction products, blends, polymers, compositions, etc. may be used as a substrate onto which other materials may be applied.
  • resins, reaction products, blends, polymers, compositions, etc. may be applied as films onto the surface of another substrate or a laminate may be produced from the resins, reaction products, blends, polymers, compositions, etc. disclosed herein.
  • the resins, reaction products, blends, polymers, compositions, etc. disclosed herein may be used in the manufacture of printed circuit boards or for general use in any electronic device.
  • resins, reaction products, blends, polymers, compositions, etc. disclosed herein may be used in radomes, antennas (e.g. cellular phone antennas, satellite phone antennas, antennas for 5G communication devices, etc.), or in radar structures.
  • the resins, reaction products, blends, polymers, compositions, etc. disclosed herein may be used as part of an under fill adhesive composition.
  • the resins, reaction products, blends, polymers, compositions, etc. disclosed herein may be used in cellular base stations, wireless base stations, modems, and routers.
  • the resins, reaction products, blends, polymers, compositions, etc. disclosed herein may be used in radio frequency identification tags and other sensors.
  • the resins, reaction products, blends, polymers, compositions, etc. disclosed herein may be used in microwave communication systems.
  • the resins, reaction products, blends, polymers, compositions, etc. disclosed herein may be used communications and network servers.
  • the resins, reaction products, blends, polymers, compositions, etc. disclosed herein may be used in backplanes.
  • Sodium hydride (60% dispersion in mineral oil) was obtained from Sigma-Aldrich. Cyclopentadiene was isolated by thermal cracking of dicyclopentadiene (Ultrene 97 from Cymetech Corporation) at temperatures of 150 -180°C per literature methods. Vinylbenzyl chloride was obtained from DOW Chemical Company and used as received. Allyl chloride, 1,3-dibromopropane, 1,6-dichlorohexane, divinylbenzene, and glycidyl methacrylate were obtained from Sigma Aldrich and used as received. Maleic anhydride was obtained from Huntsman and used as-received.
  • Methyl tributyl ammonium chloride was obtained from Sachem, Inc. Trigonox 145-E85 was obtained from Akzo Nobel. HTL-300 was obtained from Lonza. Novocure 200 was obtained from Novoset LLC. Ricon 153 and Ricon 100 were obtained from Total/Cray Valley. Sartomer CN-301 and Sartomer CN-303 were obtained from Arkema. Noryl SA-9000 was obtained from Sabic. BMPI-300 was obtained from Cyalume Specialty Products. BMI-3000 and BMI-689 were obtained from Designer Molecules, Inc. BMI-TMH and BMI-2300 were obtained from Daiwakasei Industry Co.
  • 4,4'-diphenylmethanebismaleimide was obtained from Chem-Impex International. Homide 250 was obtained from HOS-Technik. TAICROS, Compimide 353A, Compimide C796, Dynasylan MEMO, and Dynasylan VTEO were obtained from Evonik.
  • 7.5g of resin from Example 1 was dissolved in 10.0g of dichloromethane solvent and combined with a solution of 7.5g BMPI-300 (Cyalume Specialty Products) in an additional 10.0g of dichloromethane solvent.
  • the combined homogeneous solution was allowed to react at room temperature for 10 minutes, before removal of the dichloromethane by rotary evaporation at 50°C, yielding a product mixture featuring partial reaction between the two resins.
  • 10.0g of resin were formed by blending 9.0g of resin from Example 1 with 1.0g of vinyl-functionalized cyanate ester resin HTL-300 that had been catalyzed with Novocure 200. This blend was poured into a mold constructed of glass plate and a 1.6mm-thick PTFE spacer and cured by oven ramp from 75-190°C at a rate of 1°C/minute, 1 hour of cure at 190°C, secondary ramp of 190-230°C at a rate of 1°C/min, 2 hours of cure at 230°C, followed by oven ramp from 230-250°C at a rate of 1°C/min, with final post-cure at 250°C for one hour to generate a cured resin panel. Dielectric properties: Dk 2.67, Df 0.0034
  • 10.0g of resin were formed by blending 5.0g of resin from Example 1 with 5.0g of vinyl-functionalized cyanate ester resin HTL-300 that had been catalyzed with Novocure 200. This blend was poured into a mold constructed of glass plate and a 1.6mm-thick PTFE spacer and cured by oven ramp from 75-190°C at a rate of 1°C/minute, 1 hour of cure at 190°C, secondary ramp of 190-230°C at a rate of 1°C/min, 2 hours of cure at 230°C, followed by oven ramp from 230-250°C at a rate of 1°C/min, with final post-cure at 250°C for one hour to generate a cured resin panel. Dielectric properties: Dk 2.80, Df 0.0085
  • 10.0g of resin were formed by blending 0.54g of resin from Example 1 with 9.33 g of a cyanate ester containing olefinic groups (HTL-300) and 0.13g of Novocure 200. This blend was placed in an oven and the temperature ramp 1°C/min from room temperature to 160 °C and held for 1 hour at 160 °C after which the temperature was ramped at 1 °C/min to 190 °C and held for 2 hours at 190 °C. Dielectric properties: Dk 2.82, Df 0.0051
  • 10.0g of resin were formed by blending 2.00 g of resin from Example 1 with 7.86 g of a cyanate ester containing olefinic groups (HTL-300) and 0.14g of Novocure 200. This blend was placed in an oven and the temperature ramp 1°C/min from room temperature to 160°C and held for 1 hour at 160 °C after which the temperature was ramped at 1 °C/min to 190 °C and held for 2 hours at 190 °C. Dielectric properties: Dk 2.81, Df 0.0054
  • 10.0g of resin were formed by blending 7.5g of resin from Example 1 with 2.5g of an olefin containing phosphazene (SPV-100). This blend was placed in an oven and the temperature ramp 1°C/min from room temperature to 160°C and held for 1 hour at 160 °C after which the temperature was ramped at 1 °C/min to 190 °C and held for 2 hours at 190 °C.
  • 10.0g of resin were formed by blending 5.0g of resin from Example 1 with 5.0g of an olefin containing phosphazene (SPV-100). This blend was placed in an oven and the temperature ramp 1°C/min from room temperature to 160°C and held for 1 hour at 160 °C after which the temperature was ramped at 1 °C/min to 190 °C and held for 2 hours at 190 °C. Dielectric properties: Dk 2.92, Df 0.0058

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Claims (5)

  1. Résine ayant une structure définie par la formule (VI) :
    Figure imgb0099
     où :
    X est du cyclopentadiène ;
    B est H ;
    (Z)n est une liaison ;
    m est un nombre entier dans la plage de 1 à 5 ;
    et A a la structure définie par la formule (IID) :
    Figure imgb0100
    où Ra et Rb sont sélectionnés de manière indépendante parmi H, F, un groupe aliphatique à chaîne droite ou ramifiée, cyclique ou linéaire en C1 à C10 ; Y est H, -CH3, -CH=CH2, -CH=CH-CH3, ou un alcyne ; et t est 0 ou un entier dans la plage de 1 à 20.
  2. Résine selon la revendication 1, dans laquelle t est 1, et Ra et Rb sont chacun H.
  3. Résine selon la revendication 1 ou 2, dans laquelle Y est -CH=CH2.
  4. Résine selon la revendication 3, dans laquelle la résine a une structure de :
    Figure imgb0101
  5. Résine selon l'une quelconque des revendications précédentes, dans laquelle la résine comprend au moins un groupement de A se terminant dans l'un parmi : un groupe -CH=CH2, un groupe -CH=CH-CH3, ou un groupe alcyne.
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